Trisazo dyestuffs, their copper compounds and their manufacture



Patented May 12, 1942 TRISAZO DYESTUFFS, THEIR COPPER COM- POUNDS AND THEIR MANUFACTURE.

Adolf Krebser, Riehen, near Basel, and Werner Bossard, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland No Drawing. Application July 12, 1940, Serial 9 Claims.

It has been found that valuable copperable trisazodyestuffs are obtained by coupling tetrazo diphenyl and its substitution products only on one half side with an o-hydroxyphenyl carboxylic acid, then combining the obtained diazoazo compound with an amine or an amino sulphonic acid of the naphthalene series coupling in para-position, and containing in ortho-position to thediazotable amino group a substituent capable of forming metal complex compounds, further diazotising the amino disaz'o dyestufi, coupling the latter with a N-acyl-substitution product of the 2-amino-6-hydroxynaphthalene-8-sulphonic acid and converting the trisazo dyestuff, according to usual methods, in substance or on thefibre into the copper complex compounds. The new dyestuffs possess, also when coppered, substantive properties and dye green to olive shades which are distinguished by a remarkable fastness to light. If desired, the new dyestufi-copper compounds can also still be further coppered on the fibre.

The following examples illustrate the 'invention, the parts being by weight.

Example 1 18.4 parts of benzidine are, as usual, tetrazotised in a hydrochloric acid solution with 14 parts of sodium nitrite. The tetrazo solution i first coupled alkaline with 14.5 'parts of salicylic acid and then in acetic acid medium with 25.3 parts of 1-amino-2-hydroxynaphthalene-methyletherfi-sulphonic acid. The disazo dyestufi is isolated, formed into a paste with 1500 parts of water, intermixed with 7.2 parts of sodium nitrite and diazotised by rapidly adding at 10 C. 70 parts of concentrated hydrochloric acid. The diazo compound filtered off is coupled in aqueous suspension with 28.1 parts of 2-acetylamino-6-hydroxynaphthalene-B-sulphonic acid in presence of 40 parts of ammonia of 25% strength and 150'parts of pyridine. The finished dyestufl is salted out with 5% of common salt, then filtered and washed with brine of 2.5% strength.

For coppering the pressed cake of the trisazo dyestuff is dissolved in 1600 parts of water 'at 95 C., an aqueous solution of 25parts of crystallised copper sulphate is added thereto and the whole is kept for 4 hours at boiling temperature. The dyestuff is filtered 011 and converted according to known methods into its sodium salt.

It constitutes a grey-black powder which dissolves in concentrated sulphuric acid with dull violet color and in water with olive-green coloration and dyes cotton from the neutral 'Glaubers In Switzerland July 20, 1939 salt bath of olive-green shades of remarkable fastness to light. It can be aiter-coppered on the fibre without substantial variation of shade.

- The dyestuff can also be dyed directly and coppered on the fibre.

By using instead of salicylic acid an other 0- hydroxycarboxylic acid such as for example 0- or m-cresotinic acid, or instead of 2-acetylamino-G-hydroxynaphthalene-8-sulphonic acid, the 2-w-sulpho-acetylamino-, 2-maleylamino-, 2- phthaloylamino- 6 hydroxynaphthalene-8-sulphonic acid or the carbamide of the said aminonaphtholsulphonic acid or instead of benzidine otolidine' or dichloroebenzidine, there result dyestuffs. with similar properties as they are de scribed above. y

21.2 parts of o-tolidine are tetrazotised' in usual manner and combined in a soda alkaline medium on. one half side with 14.5 parts of salicylic acid. The.,o.btained intermediate product is then coupled in acetic acid mediumwith' 26.? parts of 1- amino-2enaphtholethylether-6 sulphonic acid. Thethus obtained disazo dyestufi is isolated-then stirred up1with 1500 parts of water, mixed with .7. 2 parts of sodium nitrite and diazotised by rapidly adding '70 parts of concentrated hydrochloric acid at 10 C. The separated diazo body is introduced, intoa solution of 28.1 parts of 2-acetylamino-G-hydroxynaphthalene-8-sulphonic acid, 40 parts of ammonia of-25% strength and parts of pyridinein 200 parts of water. The iormation of the dyestufi being completed, the latter is; salted'out with 5% "or common salt, whereupon the separated dyestuff is filtered off ndwashed with a'brine of 2.5% strength.

The trisazo d'y'estufi is dissolved according to Example 1 in 1600 parts of hot water and treated during 4 hours with 25 parts of copper sulphate.

' a It constitutes a grey-black powder which dis- "solves in concentrated. sulphuric acid with a dull yiolet coloration and in' water with an-olive-green coloration; It, dy'els cotton olive-green shade of good fastness to light.

Example 3 30.6' parts, of monoacetylbenz'idine monosulphonic acid are indirectly diazotised and coupled at 0 C. in a weakly caustic soda lye alkaline medium with 13.3 parts of salicylic acid. The coupling being completed, caustic soda lye is added thereto until a concentration of 5% is reached, whereupon the mixture is heated for 30 minutes up to 99 C. "The dye'stufi then saponifi'ed is precipitated out at Conga-acid reacw The thus obtained aminodisazodyestufi=-is iso=' lated, diazotised analogously td'fExaniplahcowpled' with 34.3 parts of 2-benzoylamino-6-hydroxynaphtha1ene-8-sulphonic acid" in' presence of pyridine and ammonia and isolated im the usual manner.

The dyestufi, a dark powder-{dyescotton pure yellowish green shades, whichare,h'owever,' notfast to light; by after-treating with a copper salt solution on the fibre there results a bluish-olive tint very fastto light.

By copper'ing according to Examplel in'sub stance one obtains a copper=containing dyestufi which dyes cotton bluish-olive shades of very good fastness to light.

Instead of '1-amino-2-hydroxy naphtlialene- H methylether-G-sulphonic acid may beused 1'- amino-2 naphthaleneoxyacetic acid:

What we claim is:

7 1; A process for the productionoftrisaao'dyestufis',jcomprising coupling'a tetrazo compound selected from the group consisting-of tetr'azodiphnyl and its (.ZH3-; C1- and sOaH substitution product's on one half side with an d-hydrOXyphenyl carboxylic acid, combining the" obtained diazoazo compound with one member of the group consisting offaroma'tic' amines and amino sulphonic acid; of ii the naphthalene Y seriesx coupling para-pesaion an d: containing in ortho position to the 'diaZbtisahle' al'fi'ifiiigioup a sub stituent capable oi 'forrfiirig 'metalcomplex' cohipounds selected froni tlie' group consisting of -O.alkyl and OICI-IzCOOI-I; further-'diazotising the obtainedf an'iinodis a'zo dy''stufi, coupling the same with a N-acylasub-st'itution product of* 2-=amino"-6= hydroxynaphthalene-ii sulphonic acid and con-'- verting the obtained 'tri'saz'o dyestufil intoefcopper complex compound. I

2. A process for the manufacture" of a} tris'a'zo dyestuff, comprising tetra'zotising benzidine'; cou-' pling the tetrazosolution on one half side with salicylic acid and then with l-aniino 2-hydroxy5 na'phtha1enem'ethylether fi-sulphonicacid;isolat ing'the so-obtained disazo dyestuff, diazotising the same and coupling'the diaz'o compoundwith 2- acetylamino 6 hydroxynaphthalene 8 sul phonic acid'.

3. A process for the production of a trisazo dyestuii; comprising tetrazotising" ben'zi'dine, combining the tetrazo compoundon" oneha'lfside with" salicylic acid, coupling" the so -obtained dia'zo'azo' ccmpoundwith' namino-ahyaroxy plithalen'einethylether 6-su1phonic' acid; isolating then the so-obtained disazo' dyestufi, furtherdiazotising it, and coupling" the separated diazo compound with the carbamide of 2- amino-6-hydroxynaphthalene-8-sulphonic acid.

'4. A process for the production of at'risa'zo dyestufi, comprising -diazotising mon'oacetyl benizidine monosulphonic acid, coupling the obtained compound with salicylic acid; saponifying' tlie 'acetylamino group; further diaz otising the re} sultingproduct and coupling'with 1-a mino-2-hy droxynaphthalenemethylether-6-sulphonic Jacid, isolating the obtained aminodisazo dyestuff and after diazotation coupling it with 2-benzoy1amino-6-hydroxynaphtha1ene-8-sulphonic acid.

5. The trisazodyestufls of the general formula coon ' l lHiacyl wherein .X'Imeans a substituent of the group cansistingof CH3; Cl and-"SO3H,'.Y means. a; substituent of the group consistingof'CHaand'H and Z meansia substituent of the groupcconsisting of Hand SOzH} dyeing when coppered cottongrfeen to olive shades of good fastness to light. is

6. The trisazody'estuff's of the general formula SOaH' NELacy'l wherein-X means a substituent of the group consisting of CH3; C1 and SOH; dyeingtwhen cop;- pered cotton green to' dive shades of good fastne'ss't'o' light; V

'7; The"trisazodye'stufi'ofthe formulav SOsH NELCOCH:

being, whencopperedJn theform of the sodium salt; a grey-black-powder, soluble'in concentrated sulphuric acid with dull violet color and? in Water with olive-green color and dyeing cotton from the neutral Glaubers salt bath olive-green 9. The trisazodyestufi of the formula shades of remarkable fastness to light. 00011 8. The trisazodyestufi of the formula COOH N=N- OH I 5 l N: 3OH SOaH (I)CH: OH N=N- N=N SOaH N=N N=N SOaH S0311 NH-COCQHB being in the form of the sodium salt a dark pow- SOQH NH-CO-NHE der dyeing cotton pure yellowish green shades being in the form of the sodium salt a dark which by coppering turn to bluish-olive tints of powder, dyeing cotton direct green shades which very good fastness to light.

by coppering turn to olive-green tints of remark- ADOLF KREBSER. able light fastness. WERNER BOSSARD. 

